Substituted aryloxyalkylol sulphides



Patented Oct. 20,1942 I 2,299,213,

UNITED STATES PATENT OFFICE SUBSTITUTED ARYLOXYALKYLOL SULPHIDES Elmer W. Cook, New York, N; Y, and William D. Thomas, Jr., Stamford, Conn, assignora to American Cyanamid Company, New York,- N. Y., a corporation of Maine No Drawing. Application November 29, 1941,

' Serial No. 421,035

11 Claims. (Cl; 260-609) This invention relates to new organic comor sulphur dichloride depending upon the type of pounds and their preparation; more particularly sulphide desired as the reaction product. The to alkyl and cycloalkyl substituted aryloxyalkyl -and cycloalkyi substituted aryloxyalkylol alkylol sulphides. compounds which we employ in our reaction have The alkyl and cycloalkyl substituted aryloxythe general formula alkylol sulphides described and claimed herein ox-on by us may be represented by the general formula:

OH on B1 1: 15' f R1 R1 Sun Ra in which X is an alkylene group of 2 to 4 carbon atoms such as -CH2CH2-.

R1 R: I -CHCH1 I in which X1 and & are alkylene radicals con- H:

taining 2 to 4 carbon atoms inclusive, 1:- is a positive integer not more than 2, and R1 and R2 and R1 may be hydrogen an alkyl radical of from 1 to 14 carbon atoms such as lzisrfiit methyl. R1 and at least one R: being a member of the n'amyljterbamyb ethyl hexyl' or a group consisting of alkyl and cycloalkyl radicals. cycloahphauc radmal such as cychpentyl' cyclow have found that these alkyl and cycloalkyl hexyl, methyl cyclohexyl, dimenthyl cyclohexyl, substituted aryloxyalkylol sulphides are good cor- P the f P opyl. butyl and amyl mono-, rosion inhibitors, particularly when dissolved in and f fi cyqlohexyl radlcals' lubncating oils and may be employed to great Preferably both Rs are either alkyl or cycloadvantage therein in the preparation of heavy alkyl Iadlcals- It is m le. however, to use duty crankcase oils. In adidtion to being excelcompounds in which one of the Rs may be lent corrosion inhibitors in lubricating oils the but Z resulting pmduiflts w a compounds of the present invention exhibit eased Y in lubricating 011$- detergent and dispersing properties and reduce W prefer. Prams the mmosulphldes of the the formation f sludge, ring sticking, varnish present invention by reacting approximately 2 deposition and other undesirable conditions m1e5 or an alkyl al'yloxyalkylol which develop when the lubricating oil is with one mole of sulphur dichloride (-8012) in the iected to heavy duty service. They are also of plfesence of a small 1111011111? e ample -2 value in the preparation of fly sprays, fungicides, mole, 0 anhydrous luminum chloride as catawetting agents, dispersing agents, plasticizers, other medal-Craft catalysts $11011 as corrosion-resistant slushing oils and like composi- 0 SW15, F8013, h. 1 14. TiCh, Te h, BiClz, nd mm ZnCl: may also be employed as catalysts in our The alkyl and cycloalkyl substituted aryloxyreactmn with decree-singly eflwtive l s- The alkylol sulphides of our invention are prepared 11151119111685 are p i m i the e nne by by reacting an alkyl or cycloalkyl substituted substituting sulphur chloride (S2012) in place of aryloxyalkylol compound with sulphur chloride Sulphur l ide.

. tert. butyi ethanol ride as follows:

The reaction my be. mlamm with rm...

and sulphur dichlo- (CHsh-C tn. t

Ordinarily we carry out the reaction with the reactants dissolved in a suitable solvent such as carbon disulphide, petroleum naphtha, nitrobenzene, ethylene chloride, etc. The reaction mixture with the catalyst present is then heated until the evolution of H01 has substantially stopped. The mixture is then treated with cool dilute HCl, or other acid such as sulphuric, acetic, etc., and the product recovered by extraction with toluene or other suitable solvent. The product can be purified by washing with water, in which it is insoluble, and the solvents removed by evaporation.

It will be understood of course that the preparation of the disulphides with sulphur chloride proceeds in the same way under the same reaction conditions. It will also be understood that the cycloalkyl substituted aryloxyalkylols may be Example I 56 parts by weight of 2,4,-diamyl phenoxy ethanol was dissolved in 50 parts of carbon disu1-,. phide and 10.5 parts by weight of sulfur dichloride dissolved in 10 parts of carbon disulphide was added thereto with stirring.

then-added and the mixture stirred and warmed gently under a reflux condenser on a steam bath sulphide as an orange-red oil. easily soluble in gasoline and lubricating oils but only slightly soiluble in water.

What we claim is:

' formula employed in place of the 2,4-di-tert. butyl" phenoxy ethanol illustrated in the above equation in the same manner and using the same molecular proportions.

Metal salts of these compounds may also. be.

I prepared by reacting the compounds Just described with appropriate molecular amounts of 1 finely powdered metallic aluminum, metallic magnesium turnings, calcium. metal,

etc. A small amount of mercury chloride may be added to start the reaction. The reaction mixture may be gently heated on a steam bath at first but may require cooling later .because of the exothermic character of the reaction. Metal salts may i also be prepared by heating theccmpounds described with an alcoholate of a lower boiling 9.1-

cohol, sodium methylate for example, under conditions such that the lower alcohol is driven oil.

The aluminum salts of 2,4-diamyl phenoxy efih-v anol monosulphide, for example, maybe prepared 3 by this method.

,The preparation or 2.4-diamyl phenoxy ethanol monosulphide, will now be described in dein which X1 and X: are alkylene radicals containing 2 to 4 carbon atoms'inclusive, n, is a positive integer not more than 2, and R1 and R2 are members of the group consisting of alkyl, cycloalkyl, and hydrogen radicals, at least one R1 and at least one R2 being a member of the group consisting of alkyl and cycloalkyl radicals.

2. Chemical compounds having the general formula a on on 1g: i

in which X1 andX: are alkylene, radicals containing 2 to 4 carbon atoms inclusive, n is a positive integer not more than 2, and R1 and R2 are in -which n isa positive integer not morethan 2, and R1 and Re are alkyl radicals.

3 parts by weight of anhydrous aluminum chloride was 1. Chemical compounds having the general 5. Chemical compounds having the general formula OH OH (1112 (EH:

H: H! 5 HaC CH3 CHLCHL S- .CHa.CHa

1130.03,. .(CHzMCHsh. omen;

6. Chemical compounds having the general formula B1 R: k

in which n is a positive integer not more than 2, and R1 and R2 are cyclohexyl radicals.

7. A method of preparing alkyl and cycloalkyl substituted aryloxy-alkylcl sulphides which comprises reacting a member of the group consisting of alkyl aryloxyalkylols and cycloalkyl aryloxyalkylols with a member of the group consisting of sulphur chloride and sulphu dichloride in the presence of a catalyst.

8. A method of preparing alkyl substituted aryloxyalkylol sulphides which comprises reacting alkyl aryloxyalkylols with a member of the group consisting of sulphur chloride and sulphur dichloride in the presence of a catalyst.

9. A method of preparing cycloalkyl substituted aryloxyalkylol sulphides which comprises reacting cycloalkyl aryloxyalkylols with a member of the group consisting of sulphur chloride and sulphur dichloride in the presence of a catalyst.

10. A method of preparing di-(2,4diamyl) phenoxy ethanol monosulphide which comprises heating 2,4-diamyl phenoxy ethanol with sulphur dichloride in the presence of a Friedel-Crafts catalyst until the evolution of HCl has substantially stopped.

11. A method of preparing di-(2,4-di-tert. amyl) phenoxy ethanol monosulphide which comprises heating 2,4-di-tert. amyl phenoxy ethanol with sulphur dichloride in the presence of a. Friedel-Crafts catalyst until the evolution of HCl has substantially stopped.

ELMER W. COOK. .WILLIAM D. THOMAS, JR. 

